Note: Descriptions are shown in the official language in which they were submitted.
93 WED 12:3.~ ID:CO~I-EXE~_UTI~ rEL 1`~ 6-'l6b-zl43 pQ22 pi~3
2 ~ ~ 7 9 :3 ~
NON-AQUE:Qu~ COATIN~ cOM~ITION~ FRO~ P0I.YETHYLE ME~` ~13R~PHT~LATE
R. Tomko
D. S~yr~
W. Lesney
M. Rao
.A~.:~U~KVUNl~ U~ rnEi lS~
Thi~ ~nvention rel~t~s to n~vel coatinc~ composition3 which
uti~ize polyethylene terephth~late (P~'r) aæ ~ ~aw m~terial for
pxoducing the ~ilm-for~ning resin for su~h coatinys. Most
lo p~o~ ly, tho I'E~ ~c rooyalod or :~ccl~3imcd rET f~om pl~ tio
tlr~ o~ su~h ~ two-litcr hovc:ragc bottloc.
Pl~ ~.h ~5 p~:rr ;~ nl~n~ fnr ;lhnl~t 7-R w~;~l~t r~rrL~n1, ~n~l
about ~0 volum~ p~ent, of th~ wo~ld's solld waste. As a result,
muc:h legiSl~tibn h~s been propv~d and~or adoPted re~uirin~3 ~he
reayczling OL' plastlc:s.
PET iB the prim~xy ingredient i~l ~lastic el:r tic~ u~ a~i tw(~
liter be~rera~e b~t~;le:~ Rnd the lik~. In the u.~ E~ ; the
pla~:tic most often ~ecycled. The l~iggest uses for recycled PET are
~æ flber~; in c~rpeting and insulation. ~ecycled PET i6 also used
in hatllroom equipmen~ and blow-molded b~ttles.
~xooe~ea ~or re~ycling P~T beverage bottles into u3able ~aw
)p~44;o~ o~ 7r~n~ r~g ~ o~ yoa t~ oc~ a ~l'C ~I~W~ .
~or ex~mple, ~a3tman Chemicals Pu~ atio~ No. N-~62A ~ntitled
Un aturated Pol.~e6ter Resin~ ~ased 011 Reclaimed Polyethylene
T~r~p~ha~e ~ L_~Qy~q~ Bottles, ~alendine et al. ~19~4),
te~ohe~ a prooe~ ~o~ converting PET b~v~rc~ge bo~tle~ into use~ul
int~mad1ate~ ~or the ~ynt:lle~i~ oE un~aturate~ pol~e~ters. ~he
un~ar,ur~lt~ p~ly6~6~c~ 3 ar~ ~ur~n~L- Cau~llC ~3 ~13~;tUl e~s L-~W
, , .r~"~ ' 9~3 lJ~ 2 ~ ~3 I L) COI I--F`~ ~:CIJT I I.IE I EL ~IO C~ 5~ 3 ~ F~
f~ '~1 4 7~
m~terialB for produclng unreinor~ed cle~r Cc~tings ~nd ~iber~
gla~ r~inforcsd laminates.
A ~econd Ea~:tman ChemiOal~ Publi~ation, No. ~1-2923, e~ti.tled
~ m Re~lalmed YolYP~ h~nQ~ halate, (1~87)
teache~ the re~lam~tion o~ PET for produc~ion of Aromatic polyes~er
polyol-~ which are useful in rna~ing ricJid p~lyur~than~
polyi.30cyanurate ~oams
U.5. Patent ~,223,0~ (C~rlstro~ et al.) teaches the use o~
t~e di~sti~n product o~ p~ly~l~c~lc-,O tcrop~h~l~tO ~crap~ wlth
organic polyol ~or the produotion o~ ri~id polyure~h~ne foam~.
~ .~. P~ten~ 4,417,001 ~Sv~ 1,) t~ L~ Li~l
o~ low smok~ isocyanur~te modified polyure~hane f~ams w~lch ~e
prep~red fro~ p~lyol~ which ~re th~ dige~tion product o~ ~ige~tin~
polyal~ylene ~erephthalate s~raps and or~anic pol~ol~.
U.5. Patent 4,048,104 (Svoboda et al.~ teache~ the prep~ra~i~n
o~ polyi~o~yanate prepolymers an~ polyurethane adhe3ive~ and Eoams
wherain the prepolymers ~:re prEJparE3d by re~titlg ~rgania
polyl60~yan~te wi~h polyol~ which ~re the ~ige~tio~ product of
polyalkylen~ ~erephthalate ~craps ~nd org~nic polyols.
~U~A~ 0~ TH~ INVENTI~N
~ his inven~ion relates to novel coa~ing composi-tion~ which
u~ilize PET a~ a X`aw materia~ fo.r produclng the ~ilm-~ormillg re~in
~r ~UCh ~oating~. Prerer~bly, ~h~ pr~n~ inv~ntion ~ t~s to
lo~ ~i.d vHlue~ non~a~u~oUs~ ~lir or bake dr~y ~oa~ing~ deriv~d from
rQalaimed PET and to a prO~eF.~ ~or p~oducing ~uoh coa~irl~. uslng
. , ''
Sf~ 2~ 3 I~JED 12~ co~ E~;EcllT iSE TEL 1~ :21~ f_.f,-21~ Z? P05 ~
~ 2~
reclaimed PET b~ne~it~i the ~nvironn,~r)t by ~educitlg t1l~ am~unt of
~;olid waste dump~d at land~llls. U~;in~ reclaimec~ PE~ benefit~ this
p~oce~s in that it i~ a relatively in~xpensive raw material wh;ch,
as i~ ~hown herein, produces an excellen~ col~ti1lg Gomposition.
~n ~ocordance wit:~1 -the present itlV~n~iOn, PET resln (o~ an
equ1valent polyalXylene terephtha1ate re~in3, typieally having a
structure a~3 ~nown ln FlgUre l:
O o
10 ~i~ure I OH~CH2C~2-o-C~ C-03CH2C}12011
n~100
i~ fir~t dlgested into lower molecul~r weight polymeric units
throu~7h an alcoholy~;is re~ction. ThP. rlig~ nn l~rnAIIr~t nf ~h~
15 ;al~h~lyo ~ 7 ~c~ ~ion i~3 then f~r-th~3r ~eact;e~l wlt~ nn n~ S d-
~unctional r~3ac~ant, an anhydride or an isocyanat~ to yleld a resin
cotnpositio~ suitable ~or use in coating composl'cions~ By varying
the a~un~3 and type~ o~ aciA~, isocyanate or hydroxy-~urlctional
reactantE: according ~o the te~chlngs herein, one can formulate. a
20 variet~ of c:oatings sy~tems i ncludin~ polyure-th~r1es, high acid
value, water-reducible cc>ating~ and low acid value, solvent-based
coatin~s. Additionally, fu~ther chemical modi~ications are
appllo~ble And ~re further exe~npli~ied h¢rein.
Aocordingly, it i8 ~n obj~ct of t:hi~ invention to teach the
25 u:s~ o~ polye'chyl~ne ~rephthalate a~i a ~aw mate~ial fo~ the
production o~ coating compo~itic:n~.
' L~ 3a l L,t'pt . r~ 5~ 70~ ~lall ~(J,~13 ~:34 ~lo .()~ P.~3
1~ is a ~rth~ o~l~ct of this in~ention t:a t~ach no~
air nnri ba~e dry coatir1~J colnpositlons whic~ utiliZ~ reclaimed ~E~r
a~ a r~w material.
l`hese and other o~ject~ will hecom~ mor~ r~adily ~ppar~nt ~r~m
the det~iled descripti~n, ~xa~pl~ and clai1n~ whlch eollow below.
DeTAI~EG DESCRIP~ION OF TIIE IN~tE2~TION
As statcd ~bov~, the prcsen~ ln~en~.lon rcl~tes to novel r~on-
aqueous. coating composition~ compri~ing rET as t11e starting
~ateri~ll eOr the proc1u~tion b~ a fil~-for~ing resin.
l. PE~ ~OURC2
The ~tual so~1rce of PET us~le her~in is not o~ critical
~mport~nce to this invention. "Virgin" P~T, ~hat is P~T whic~h is
a~lmercially produced specificall~ as a raw n~aterial, is a~cept~ble
Prom a c:hcmic~l standpo~.nt for USQ herein I.ikew;.se, r~cycl~d or
r~ol~im~ PE~r tF. a~ceptable ~rom a chemic~al stan~oil1t. At th~J
tlme ot thls ap~l:icatior., there a~ advant~ges to t}l~ ~n~ironmcnt
~r~dl~ction o~ solid waste) ~n~ to the eCO~01~icS o~ this proces~
. (recy~oled PE'r ls much l~ss expensive than virgin ~q') by us.ln~3
; ro~ led or rcclai~ed PE~i and, there are no perf~rmarlce
di~adva~ta~es~to usiny recycled PEI' ver~Us vir~in PET. As ~
~onsequence, recy~led or rec.Laimed PET i8 a preEerr~d ~t~rting
mat~ri~l though l~ ~hould be appreclat~d that any s~urce oE
~el~tlvely pur~ PET i9 acc~t~ble.
Typi~lly, ~h~ ~ourc~s foL PET are n~any and varLed. one
~o~Jrc~ ~f olther ~lr~in vr ~bcycled P~l' is mat~lrial ~ro~
R4 -~ R4
''; ' ., :
'' ' ' ~
' '' ', ' "' '',
~) l P ~ J P ~j r r -:1 . .? I t~ f) - I ~ ~ h ~ O . ~ ;~ 1 8 ~ i l! . O ;~ ~ F . O ~
f~ 8r~
~olym~ ma~ acturels. A ~ec~n~ ~ource c~f P~,~J 1s ex~:e~;s E~l r ~r~Jn~
th~ op~ri~tion~ of th~ bcv¢ra~e bottL~3 man~lf~lct~2rers. i~ t~lird
~ou~c~, ls privatc ¢n~ pr~neur~; deal lng ln recl;~llmecl PE'r. A f~lurth
~oll~.ce ls ~om~ nity recla~natlLon ancl recyclin~ cent~r:s. t~ pref~-r~d
5 ~;~urce Or PET l.q r~yc:led PET be~ert~go bottles.
~ or purposes of this invention, the PET ~ ould be provi~ecl in
~ con~minut~d form. It can be fl~keci, graJ~ul~t~ t o~r.d to ~3
powdel~ or pellQti~ed. Praferred i~ fl~ cl PE'r. T]-e only
corl~;traint placl3d on the PET at t~lis po1nt is that lt is rel~t.i~ely
10 pure; th~t i6, th~re ~hc>uld not be ~ lQvel of impurities above
a}~out: vn~ ~1) w~l~ht p~rC~11t nor should ther~ bc a~ y appreciAhl~3
lcve. of impl~ritic~s whi~h ~re ch~mlcally re~:tive wit~in this
pJ~oC~e~;s. F~ET whlch i.s acceptable tor tlse herei~1 ~3ho~Jld hav~3 the
t'~ owing ah~lracterl stic.s:
Intrlnslc vlf~cosity 0. ~5-0. 75
- M~is~.~rf~ ~cl . 09~
~ Lo?: ed PE:I' conterlt <~ OOpprn
High ~0n6i.ty Poly-
et~ylQnQ ~13L)PE) clOOppm
Adhe~ive~ c50O~ m
Alumi num ClOp~m
2~ C!}l~I8TRY OF PET
PET 1~ npril3ed of rep~atln-J units of ethy1eoe qlycol an;i
tere~)htha~ic acid connecte~l by cster 1in,ca~s~ Fiyu~e I, above,
~5 shows a typical P~T mo1ecu1e. E~ch rep~c-t:Ln~ unit of PET has a
weignt ~v-ara~e mol~culAr wo1clht of 1~ with one equiv~1ent ~f
et:hy1~ne g1yco1 and on~3 equiva1etlt of terephthAl.tc acld. By
raa~l:ir\~J P~T with ~ith~ ~n alcohol or wlth an ~ICi~l, it il!; po~i~lb1
t;c re~ c~ thcl av~r~ga ch~ln l~ng~.h Oe t:he ~F,'r nlc~1ecu10~.
> ~ 4
, . ,., .:, , ",
: .
: ;, . . :
J~ 2~)-'9~ ED 1, :~13 ID:COII-EXFCUTIUE rEL i`lO:ZI~ 2kl~ t~
( , .
. Alooholy~ls of P~T
~n~ cheml~l.ry o:t P~l' 15 ~uch the~t e~n e~qullibrium exlss;~3
b~twee~ PE~, water, ~th~len~ ~lycol (E~) an~ ~es~sphthalic ~oid
~TPA) . ~hls aquilibrium ~akes it possible t~ ~b~antially revers~
the polym~rizatlon pro~e~s and depolymers ze PET inSto its star~ing
m~erial~. The E~t~sars Chemiaal publications ~ite~ ~bove refer to
the procs3ss of depolymseri~ing PET as ~lycolysiS~. That prooe5s
.oom~rise~ the catalytic re~ction o~ PET with a polyol. As ~urther
de~inad and exemplified below, it should be apprs~ciated that
o hydroxy-funotional ~naterial~ ha~i~g OH f~nct~ion~lity ~rea~er or
le~s than two can be eEfec-tivPly utili~ed in the pr~.s~n1; p~ocess;
thu6, the prese~t pro~e~ is h¢rein referred to a~s "alcoholy~i~5'.
Ih th~ ~ontext of ~he present inven~ion, refere~ce to "~ ohol"
~hould be under6tood to refer to ~oth mono- and poly-funotional
15 alcohols unloss speciflc~ t~ught otherwis~.
~h~ numbe~ o~ O~ e~uival~n~ Ero~ the alcohol should be equ~l
to, or ln excess o~, the numbe~ of equivalen-ts of ethylene gly~ol
from the PET. Pre~eral~ly, ~he ra~io oi~ equivalent~ 6hould be
betwe~ out 1:1 t.o ~h~l.lt ~1, more. ~refe.r~ly ~hnllt. I~ h~llt.
Zo 1. 5 :1 mc les ~f OH equivalent~ per mole of PET ~
8uitabl~ catalys~s ~or al~oholysis of PET inclucle the
traclitional ~r~nses~e~ ation catalys~: inc~udiny ~tannous
octoate, c::alcium hydroxld~, c~ m ~onna~e, lithium hy~roxide.,
bA~iU~l hy~roxi~ dlum hyd:rox.ide, ~odiulll m~thoxide, mangane~
25 ~ ,t~3 tetrahydrn~ nd polymeria di.oryanotin Cat~:,1Y6,t6~L 5Ue'tl as
d~b~.yl tln ~id~ ~r~d~mo ~ t, Qv~ilabl~ from M~ Ch~mi~al~).
, ~
:', ~ . .' ':
S~ ` . . . ?~ Er~ ~I~!--E~ T 1"~ ~
~ ~ U ~ 3 ~
Most pre~erred i~ dlbutyl tin oxide. IP used, the catalys~ should
bç~ pr~3s~nt in an ~mo~lnt of from a~out 0. 2 weight % to ~out 1. 5
weight % based upon th~ total w~ig~t o~ the ~ET and al~ohol.
When PET and a alcohol are react~d togeth~r in the pr~s~nc~
of ~he above cataly6t ~nd heat, tha high molecular weight PET
m~l~ d~r~ ;o o~ r t~ ir~ W 5'~
aocompliehed ~hrough chaln attack and excll~nge `oy thc al~ohol with
the ethylene glycol units of -~h~ PET mole~ule. This ~ttack ~d
exchan~e con~inUe~ ~o occur ~ntil a new equili~rium is established
b~tween the PET, the ~horter ~hain leng~h PET, the ~horter chain
len~h PET sub~tltuted wit~ the alcohol, the alcohol and ethylene
glycol. Fi~ure II shows the typical produc-ts of alcoholysis of
PET W~th a repre~entative polyol:
Figure I~
~ o
HO-R-C O-R'--OH ~ Ho-R"-OH ~ Ho-R-C-o-R"-oli ~ ~lo~R'-OH
A8 ~an be ~een from Figure II, subsequent ~o alcohvlysis all
~lnQ~ning PET x~agm~nt~ nl~d prod~lct~l in ~lLlibri~lm th~wi~h ~r~
hydroxyl ter~inated As described ~urthe~ bQlow, they can be
reaatod with aold~, anhydrlde~, fatty acids, isocyanate6 cand the
like to ~o~m excellent coating compositions.
Alcoh~l~ ror u~e ln Al~oholy~is o~ PET
ry~lc.~ly~ ~hO ~lo~l-ola wlll h~v IIU~J~- ~v~y~ mol~
2~ w~igh~ o~ b~low about ~000 and typiaal numbQr av~raga molecular
w~lgh~ will ran~e ~rum ~ tt 30 ~.~ a~u~. ~o~o, an~ ecl~.ly 100
. , .
~ N- c'O-- ~ Wt L~ l c ~ l I U ~ t.X.tl~.U ! I ~Jt I tL !~(U c~ l b--~bt.~ lc~' ~
to 7~bout 400. Mothod6 of pr~paring al~hole ar~ w~11 kn~wn ih -the
:~Y~ d ~7. O~ m~ hc~ r~~ r~ ~h~ G~1 ~h~ a ~ a ~rlt r~~
to the pr~ctic:e of this invel tion.
5uitable al~ohols lnalud~ the Cl-C22 linear and br~nched
~atura~ed and unsaturated alcohol~ includin~, ~or exampl~,
me~hanol, sthanol, propanol, 'outanol, hexa~ol, linoleyl ~lcohol,
tr1methylolpropane diallyl ether, allyl alco~ol, 2-mercapto ethanol
and ~-he like. Additionally, usei~ul alcohols ln~lude the
IIY~L~XY--r~ ctiol~al Foly~-t~rs;, poly~t~3-s, p~lyu~-eth~nes,
polyaaprolacton~;, otO. a~ gQnor~lly discu~:.ad in S:~tic~n~
th~ough a.l.e. below.
a.1.a. saturated ~nd ~nsat~r~ted p~lyol~ lude
gly~erol, castor oil, ethylene glycol, dipropylene glycol,
2,2,4~trimethyl 1,3-pentanediol, n~opentyl glycol, l,~-ptvpanediol,
1,3-propanediol, 1,4-butanediol, 1,3-butanediol, ~,3-butanediol,
1,5-pontanediol, l,~-h~xan~diol 7 2, 2-dim~thyl-~, 3 -propanediol,
Bisphenol A tetraethoxylate, dodecahydro Bisphenol A, 2,2~-thio
~i~th~nol, di~ethylol propionic acid, acetyl~nic diol~, hydroxy-
terminat~d polybutadiene, 1,4 cyclohexanedi~ethanol,
20 1,2-cyclohexanedimethanol, 1,3-cyclohexanedi~eth~hol,
if3(2-hyd~oxy~thoxy)cyalohexane, trimethylene glycol, -tetra
~thylQno ~l~ool, ~ontnmothyl~no ~ly~ol, hox~m~thylon~ ~31y~
doa~mo~hylono glyool, ~iothylone glyuol, triothylana c,llyvol~
t~tr~ yl~n~ ~ly~ vL~u~l~yl~ ly~vl, l,~ c~
25 1,~-benzeno~lethanol, ~ nethyl 2-et~lyleneh~xAn~-1,3-diol,
3-~ut~n~ diol, and pol~ol~ eu~h a~ trim~hylol~than~,
~"' ' ' .
trimethy101~opane trim~thylo1prop~n~ mono~llyl ~3~ `e7?
tri~othylolh~-7X.3ne, trir~thy101propan~, 1,2,~.-b~tanctr1~ YC~LO1,
p,~ntaery~llrlto1, dipent~erythritol, e~o~,
~ b. Po1yether polyol~ c~rc~ w~11 known in thc clrt .~nd
dr~ cor,ve~)ient1y p~ep~red by the re~ctiorl J~ a diol or pc~lyol witl;
thc corre3pond1ng ~lky:Lene oxide~ Tllr~se mclteria1s ,-~r~o~merc~ 11y
availab]e ancl mny be prepa~cl ~y ~ ~nown ptocess ~uch as, for
n:~n~ple, t:hc~ proce~s~. dcsoribed in F,ncYc~o~erii~ c~ h~mic~1
~o~ c~ly~ Volume 7, p~ye6 257-262, publlshed L~y ~htt~sci.?nc-e
Pub1i~;hers, Inc., 19~ cn.~re~en~a~ive ~am~ s incllldc t~l~
po~propy]ene eth-~r c~1ycols and pc)ly~thylene ethe~ g1ye~ such ae.
tllos~. ~,3-~et~ as N:rAX Po1yols from Union Ca~bi~e ~or~oratio
~ .l.o. Another u~eru1 c~ s of hydlox~ cc.io,~
pc.1~nrs are t.~l~ose pr~p~r~d by co1ld~ c~tion po1ym~ c~tion r~.~c:t:inr
t~chniqlles as ar~ we31 known in tl~Q ar~. ~np.r~2selltclt1v~
c<-ndenq3~ion po~ym~riz~tion 1~a~t.i.ons incluc1e po1y~ter~ rc~p~1ec
~y th~ condenf;~tion o~ polyhyd~ic alc~ohols an-l po;,yc.~rhoxy!.lc a~idr
or anhyd~ides, with o~ wltho~t the inclus10rl o~ drying oll~
sem:L-~1rying oi~, or nc~n-~ry1~g oil ~Atty ~cids. 8y adjuc.ting t.he
2~ st4~c~l10metry o~ the a1cohols ~nd th~ aaitls Whil~ maint~linin-J ~n
~Xc~..5 of hydroxyl grouE~, hydroxy-functlon~l pc)1yest,ers Can ~e
readily produced to provid~ a wide rang~ o~ de~irecl mol~?cul~1r
weight6 ~n~ ~erfbrm~nce characte~istics.
Tlle polycsL~r E)olyoLs are d~rlv~d l-rorn one c~r mar~ Elro~lat.i~
25 an~lJvr aliE)~I~tio pol~cal.boxy.l..ic ~a:Lcl.~, th~ an~ d~?~ t:h~?r~of, ar,c~
~ne or Dlore a.ll~ atl.cJ and/c~r ~rom~:ic p~ly~ c,~arl~c)xy~
.;
,''' ',' ' :''
' ~.
J6~1-al3~ l/FD IZ:.la ID ~n~l E~ECUrl~)E rEL ~o:al6 566-21~13 I~O.. Fl. ~--
aaid~ includ~ the satur~ ar~d uns ?.turated polycarboxylic acids
and the d~rivativefi thereof, ~uch as malei c acid, fu~ ic acid,
~:ucc: .~ n lc. ~ ç .~ ci lp .~ icl, n ~ n~ ~r)t~ n f!
dic:!arboxylia a/:~id. 'L'h6~ carboxyl iQ aalds al~:o inalude the aromatlc
5 polycarbox~lic acid~, ~uch as pl~th~lic acid, isophkhalic ac:id,
tt.~rF2E~hth;~l 1a ;~ci.d, etc. Anhy~r~r~eF~ e~ m~le~n ;Inhyr3rl~
p~thal~c anhydride, trimellitic anhydride, or Nadic ~Sethyl
Anhydrid~ (brand nam~ rOr methyl bicyclo t 2 . 2 . l ]
h~pt;c~--2, ~)--d~ cAa-l~oxyli~: n~hy~ lc i~~ lbL~ 11 al~ 4e~ u~
Reprç~sontativ~3 saturated and unsaturated polyol~ which can be
reacted in stoic::hiometric ex~ess with th~ carboxylic acids to
produce hydxoxy-~ullctional polyesters include the diols taught in
a . l. a . and a . l . b ., above .
Typica~ly, the reaction bet~een the polyols and the
polycarboxylic a~ids i5 conducted ~t about 120-C to ~bou-t ~Q0C in
the pre~ence of an e3teri~ication ~at~ly~it such as dibu~yl tin
oxide .
a.l~d. Ac~di~lonally, hyciroxy-funotional polyllle~ can ~e
pr~pared by the ~ih~ op~nin~ rQao~ioh c)f ~poXid~E; and/or
20 polyepoxide~i; with primary or, pr~3ferably, seoondary amines or
~olyamine~ to Produce hydroxY-fUnC~ional polyrner~ Repre:en~.~tive
aTnine~ an~ p~lyamines include ethanol amine, N-methyle~hah~l amln~,
dl~n~thyl am~n~ ~ Q~hylene diam:ine, i~ophor~ne di~mine, ~to .
Rspre~enta~lv~: polyspoxides lnclude tho~e pxeparF3ù by c:onden61rlg
25 n p~lyhyclrlo alc~hol or polyhydric ph~nol with ~n epihalohydrin,
~uc~h ~e ~pl~hl~rohydrin, u~ua:lly uncle~ alk~line c~ondition~. Some
, ~ ? 4 r~ ? 1~ T 1 E I ; ~ f,h - I, ~ 3 l, ,~J ~3 ~ 3
of th~;c~ corl~ler~satlr n product:~: ar~ avAllahlra collltr131c i;~11y n~d~r.~ 3 1 f~
dcsLr~natlo~ t EPo~l ~`ron~ Shr~ll Chomlo~l ~'vmE)~ny, ~nd mr~thods ~f
pr~p~r~t.ion ~re rQprl3sentc~ti~"aly taur3ht in U.S. ~,~tel-ts ~,592,5Go;
2, 5~, 9F~5 ~ 2, 6~4, 694 .
S a.1.~. ~ther u~Cul hydroxy~furlctior,z~l pol~me~-~; c~r~ be
pLepa~ed by tho reactic~n o~ an r~lxc:es of at l~ast ~rne al~ o~lol, X~
aa t:hose ~epre~ent~ltively r~e~c~lblod ~bove, ~ h .isocya~ .e. to
prc,duce ~ydroxy-runction~l urethAncs. Rr.~;r~sent~ttive ~not;o-
~uncl:ion~l i.s~Jcy~ndte~ clu~lr~ ~llyl isor. yanatr~ ~nrl tolulyl
10 i~ocyan.~te. ~?c:prr sent~tive polyisocy.snates i~c~ r.ie th~ ali~h~tic
c~ pr~ullr~; S~IC~I a9 ethylene, trimethylenc, tet~-.tmetllyl~ne,
pe,ttantethylene, hexamethyle~lra, 1,2-propyl~lie, 1~2-butylene~
2,3~butylene, 1,3-butyleno, ethylidene Rnd but.ylld~ne
~.iisocyanatr~s, th~ cyclo~lkylene COl:lpOUh~3s s~loh as 3~ cy3n~to
methyl-3,5,5-tL-lmet~ .yclohexyli60cyan.~tr, ~ntl tne
cyclopentalte, 1~3-cyc~ohexflne~ Al'id ~ ~CyGlOheXrll~e
dii.~oc~ na~.~as; the flrom ltic ~ompounds ~uch a.s ht-pheny1.elle,
p-pl~enylene, 4,~ diphenyl, 1,5-nz~phth~ a ?In~ -n~phtl~.lIe~na
diiE;o~ y~ ;.ttes: the a].iE~hntic-arom~t:ic comprJl~ncls suç s
20 ~,4'-dlph~nylene methAne, 2,4- or 2,~ toluene~ I'-tol~lidine, ~r~
1,4-xy~ylene di.;socyanat~s; benzen~ 1,3-bis (l-i~ocyan~to-1-mcth~l
ethyl) J thc nuol~r 6ub.c;titut.ed arvri~ati~ coinpou~ uc:h dS
dia~ lln~ dl laocyanate, 4, 4 ' ~dipllenyl~ther di.lfiocyanAt~ ~nd
a~lorodi~llenylen~ di.L~o~y~n~ste; the trii~ol~y~r~cltes such a~3
trlphenyl n~ot.hane~ ',4''-tr.Li~l~cy~nclte, 1,3,5-krll~oc~ydll~t~
~n7.ene an~l 2,4,6-t~:iiso~y~ te tolu~ne~ an~ tr~lsocyarltltfa
Il
f~4 - ) fl4
' ~' ' :
~ 22-93l~ED12~ CO~ E~E~UTI~E TELI~O;~ 7~,-Z~ 2P~
2~7'~
s~lch a0 4,4'-diph~nyl dim~3thyl me~han~-2/2l~srs~-t~traisocyanatQ;
th~ polymeriz~d polyisooyanates such as tolylene dii~ocyanate
dimers ~nd tr~m~rG, and o~.her variou~ p~lyl~ocyanat~ containing
b~ur~ , ureth~n3, and/or allophan~te linkage~. The i~ocyall~t~s and
th~ alcohol~. are typiaally r~acted at tan~peratures of 25C to abou~
l50C to form the hydroxy-funational polymers.
E~p~ially pr~rrod hydroxy-ful~ation~l ~at~riala in th~
r~r7~tlr~ n~ 1~h i q i nv~nt -i ~7n z~r~ m~n~--flln~t~ n;~ l r~hnl ,c: ~:tl~h ~.c
tr~methylolp~opane dlallyl ether and allyl a].cohol; and diols and
triQl~ such as e~hylene ~lycol, dipropylene glycol, 2,2,4-trimethyl
1,3-pentanediol, neopentyl glycol, 1,~-propanediol,
1,3-propanediol, 1,4-bu-tanediol, 1,3-butanediol~ 2,3-butanediol,
1,5-p~ntanediol, 1,6-hex~nediol, 2,2-~imethyl-1,3-prOpane~iOl,
1,4--cyclohexa7leclim~t.h~nol, 1, 2-eyclohexan~a~im~athanol,
1,3-~y~ ~x~ tl~ (2-lly~L~Lll~xy)~y~lull~
trimethylene glyool, t~tra mekhylene glycol, pen~a~ethylens gly~ol,
hexamethylene gl~col, ~ecamethylene glyool, dle-thylane gly~ol,
triethylenQ glycol, tetraethylene glycol, ~or~ornylene ~lycol,
~ bel~z~n~dim~thnnol, 1,4 -benz e n ~d~h~ h ~ 1,
2,4-dimothyl-~-cth~lonohcxanc-l,3-diol, 2-bu~n~-1,4-diol, and
polyols such a~ trimethylolethane, trimeth~lolpropane,
tri~eth~lolpropane monoallyl e~he~, trime~hylolhexahe~
triethylolpropane, 1~,4-but~n~riol, ~ly~erol, penta~ryth~it~l,
dip~llta~rythri.tolJ and mixtur~s th~reo~.
~5 MOG~ pr~err~d ar~ trimethylolpropane ~lallyl ~t.her, propylQne
~l~ool, ~thylene ~lycol, dietllylene glycol, and mixtures thereo~.
,
.
. , J~ ~Q-'q3 I,IEtl l2~a~ O~ EXE,-U`rlllF TEL ~`~0 2l6-'.C~ 2L~3 t11~122 Pla -
It ~hould b~ ~pp~ci~ted tlla~ other alcohols ~hould be con3idsred
equlv~lents o~ tho~e nam~d here:Ln.
b. E~urt~ eElc:tio~ of th~ Alooholy~ Protluct~
As discuss~d ~ ly abov~, the p~oduct of the alcuholysis
reaction ls furthe~ ~eacted ko produce a polyester p~oduc~t u~eul
ln a coating compo~ition. Sin~e the alcoholy3is reaction products
~re hyd~oxy-~unctional, they can be ~ur~her reacted with
anhydrid~, aclds, fat:~ ac.ids and isocyan~tes including those
taught h~low to produce exceptional coat.i"g compositlon~. By
10 controlling the level~ and amounts of x~actants, a~ d~ us ~d
below, on8 can formula-t~ either high aoid value or low a~id value
~y ~ems rom the ~lcoholysis reaction produc-ts. The p~oducts of
su~h ~action~ lnolude alkyd~ and pol~esters which can be ai~ or
bake dried or Which can be furkher mixed, reaGted or tnodifled to
1~ r,reake di~per~ion~ o~ emul~ion polymers using the alkyd~ or
polyesters as dispersing medi~ and acrylic modifiQd alXyds and
poly~33tsrs .
Suit~ble ~cid-f~nctional ma-terials include mono-fun~tion~l
~ u~ e~ i a, c;rcJtc)~ l i~ a ~ a~ J~ vi-~y
z~ ~n ~ld run~1-lur~ ty ~ v~r~ v~ two~ p~lt~
aaid, auccinic aoid, adipic acid, azelaic acid, maleic acid,
~umaria acid, trim~llitic acid, trime~ic acid, naphthal~ne
~;llO~lrll;)OXyllc ~lClQ~ arooxy~ n~ecl polyo~l~aalerle, ~enzopnenone
tet.rn~nxboxyll~ cl1allhy~xide, ~ clicabclxy d1phelloXy e~hane, ~nd
~B tho hydroxy carboxylic acid~ of pi~al~one. oth~r ~itabl~ ~id~
include the sa~ur~d ac;id~ ~uch ~ b~tyric, capro~c, ¢~pryllc,
13
,'. :'.''
,
.
.... J~ 20-'93 WED 12:~16 ID:CO~~EXECIJTIIJE TE L 1~l0:~15~ 66--21~l3 ~c2 Pi5
~, J ~
~ pric, lauric, myristic, palmitic:, stearic, lZ-hydroxy~;te~ric,
arachidic, behenic ~nd lignoceric acid~; the unsaturated acids sucll
pal~itoleio, ol~i~, rlcinol~io, linc~lel~, linolehic,
~leo~te~ri~, licaric, gadoleic ahd Qra~ic acid~; and th~ oil~ tand
thcir fatty acid~) ~uch a~ canola, rapes~ed, castor, dehydrated
ca~tor, coconut, cof~e, corn, cottonse~d, fi~, lard, linseed,
vticica, palm ~ernal, peanut, perilla, sa~lower, ~oya, ~un~lower,
~llow, tung, walnut, vernonia, tall and m~nhaden oil~ and blends
and mixtures o~ natural ~nd synthetic oils ~nd fatty Acids,
- 10 p~rtiaularly thoae oils and fatty acid~ with high iodir~e nun~er~.
P.epresentative anhydrid~s include, phthalic anhydride,
3-ni~rophthalic anhydride, ~-nitrophth~ anhydri~le,
3-flourophthalic e~l~hydrid~, 4 chlorophthalie ~nhydride,
t~trachlo~ophthalic anhydric~e, tetra bro~nophth~lic anhydrlde,
~etr~ydroph~hall~ anhydride, hexahydro phthalic anhydride,
~e~hylhexahydrophthalic anhydride, ~UCCitliO an}lydride,
dode~nylsuccinic anhydride, oc~ylsuccinic anhyd~id~, maleic
anhydride, dichloromaleic anhydrid~, gl~lt~ic anhydrlde, adipic
anhydridc, ohlorendic anhydrl.de, lt~conic anhydride, ~it~a¢orlic
anhydride, endo~methylenetetrahydrophthalla anhyclride,
c y c l o h e x a n e ~ a x b o x y l 1 ~ ~ n h y d r i d e ,
4 - a y c 1 o h e xe n ~ ~ 1 , 2 -d i c a r b o x y l l c a n h y d r i d e ,
4-~thyl-4-qy~loh~xen~-1,2 dicarboxylic anhydr.ide,
b o r n e n Q - 2 , 3 - ~ i c ~ r b o x y 1 i c a n h y d r i d e ,
~$ 1,4~ayclo}l~xacllene~ dica~b~xylic ~nhydride,
-- Y~ WeL~ 4~ lU:UJII~ UI IV~ ItL ~U:~'lb--~t~
- ~ 3 g 7 .~ ~ ~
1~3~y~lopentan~dicar~oxyllc anhydrlde, diglycolio acid anhydride,
and the lik~.
Other u~e~ul anhydrides include those anhydrides having A ~ree
carboxyl ~roup ln a~ditio~ to the anhydride ~oup such as
trimellitic anhydride, acon.itic anhydride, 2,6,7 naphthalene
tricarboxylic anhydride, 1,2,4-butane tricarboxy~ic anllydride.,
1,3,4-cyclopentane tricarboxylic anhydride, and the liX~.
It should be Apprec.i~t~d thnt other ~cid5 ~nd anhydrides
~hould be con~dered ec~ivalen~s of those named herein.
The aoid- ~ anhydride functional material will generally have
a number average molecular we~ght below about 200V. Preferably ~h~.
aaid- or anhydride-~funa~ional nla-terlal will have ~ num~er average
molecular weight o~ b~l ow abou~ 4 00. Typioal nu~ber aver~e
molecular weight6 oP these materi~ls will ran~ f rom about 96 to
about 400.
E~peoially preferred ~ids ah~ anhydrides include the vegetable
~atty acid~ de~c~lbed above and trimelletic anhdyride.
. High ~ Low Aaid vAlue ~ro~uat~ using the AlOoholysi~
Roaation Pro~u~ts
;,r~ A~ ~t~ed ~bD~e, th~ alcohol~sis re~ction products are ~urther
rea¢ted with aaid or ~nhydride ~unctlonal mat~ial~ to produc~
either high or low acid vallle produot~. ~or purpo~ of the
~r~s~nt invention, the term "hi~h ac.icl value" i~ meant ~o be those
r!~mp~sltion~ h~v1n~.7 ~old vr~lu~ c3rea~r ~h~n l~out 30. ~he ter~i
"low acid val ~l~t~ is m~nt to be ~ a ~ompo~ ns haviny aai.~
lo~r than ~o~ ~0. C~mpo~ition~ h~ving acid values
, .': " ' ' '.
Jh~ 20~ 3 l~JED IC':'18 Irl:~O~ E~;ECUTI~)E rEL 1~ 6-5f~ 2l'l3 t-l~lZ2 P17
batw~en about 20 ar~d a~out ~o tend to exhi}~ cl-~ract~ti~;~ic~: of
both high and low acid valu~3 produat5 And, thu6, are not
cat~gori~ed as ~it;her high acid valu~3 or low acid value, although
it should be ~ppreciated thllt with some: tri~l and errcr such
5 co~apo~ltions may be acc~3pta~le itl eitl~er c~ateS~o~y.
As a guldeline, in order to for~nulat~e an alcoholysis reaction
}~rn~lr~ l-n ~1 h;~h ~ r~ P nf h~ h~1~ n~l A)~ llt fi~;, thc.
~ollowing stoichiometric proportlons (in mole~; of e~uival~nt:s) of
m~t~rlalE; ~hould be u~;ed. For ~ach mole of YET used, ~rom about
10 1. 1 t~ bout 1. 5 moles of OH should :l~e used in the alcoholysis
reaotion, ~ollowed by furth~r reaction with about 1. O to about 1. ~
mole~3 of acid or anhydride. Preferably, the moles of OH to PET
should be abou~ 1.15:1 to ahout 1.3S:1 and the moles o~
acid/anhydride to P~T ~hould be abo~t 1. O :1 ~o about 1~10 :1 for
15 su~h hi~her acid value products.
In ordex t~ formulate an ~lcoholysis reaGtion produc~ ts: a low
aaid value of less than ~bout 20, the following s1:oichlom~ric
propor~lons (in moles of equivalents) of materials should be us~d.
~or ~3ach mole of PET used, l~rom about 1. O to abou~ 1. 35 mol~3s o~
20 OA ~:hould be used ln the alcoholysis reaction, vllot~red by further
reac~tion witn about t~.~iO to about 0.75 moles o~ acid or anhydride.
Pr~laP~rably~ the moles of o~ t:o P~T should ~e about 1:1 to fl~OUt
1.2~:1 And the moles o~ acid/anhydridQ to PE'~ should be abo-lt
0.50~1 tn A~out 0.65:1.
~5 ~. Fln~l Co~tl~g Prclduata
16
' ~ , . ;
:
. J~ 2~ wE~ 12~ u~-Ex~ Jrl~lE rEL ~`io:2l6~5~;f~-zl'l3 ~1~2Z Pl8
The products of Sec~tion 2 . c. can b~ U~3d by themselve , in
ccmbin~io~ ith oth~r w~:Ll known coatings aclditiv~s, includi.ng
p1~ment~, flrw ~n~, c~ta1y~t~, Ai~ nts, ~h1v~nt~, u1tr~vio1et
light ab~o~b~rs, and th~ 11k~, or can be. fu~ther mixecl, r~acted o~
modi~ied ~ de6cribed be10w~
The high acid va1ue produ~ts (that is, acid va1ues ~reater
than about 30) of Se~tion 2.c., or such products in combin~tion
with the above-described additive~, can ~ perBed o~ ~educed in
~ater once neutra1ized with a weak b~e solution such as a tertia~y
amine in water. Neutra1ization techniques are well known in the
co~tings art. In a pre~erred embodiment, the high acid value
~roducts of Section 2 . c. o~n be redu~ed in water and thereafter
~exv~ a~ the 6tabilizing media ~or the emu1sion po1ymeriz~tion oP
acrylic and other ethy~ enioa11y unsatu~ated monvmer~/ inc1~ding
~yl.ic ~dditioll mon~mers, o1i~ne~ a~ld polym~r~: parti~ula~ly o~
or more ~lkyl ~st~r~q ~f ~ryl1~ ~ nr m~hArryl~r ~r.i~-
optiona11y to~ethe~ with ~ne or more other e~hy1enica11y
un~3aturated monomers.
Suitable acxylic e~3ter~i lnclude methyl (meth~ ~cryl~te, ethyl
20 (Jneth)acrylate, propyl ~meth)acrylata, butyl (meth)acrylate,
hydroxy ~thyl (m~th)acrylate, 2-ethyl hexyl (math)aaryl~te,
~crylonltrlle, a~ryla~lde, vlnyl poly~ers suoh a~ polymer~ oi'vinyl
e~er6 of inorg~ni~ or o~g~ni~ acid~, includ~.rlq vlnyl chlori~le,
vl~lyl ~oekat~, vinyl proplon~t~, vi.nyl tolu~ne, eka., ~tyren~., anc~
Z5 m~ xtu~ s thf3reoP .
, n ~,! m l . e q J I I I P P t . I E I: ~1 6 - 'i G 6 - 17 (~ 1 ), .3 ~ f (n-~
~ v ? 7 ~
E~ul~ic>rl pc)ly~n~:ri~,ltion r~actLon ccn~lt l(--n:~ are t~e] l kr)~ a in
kh~ art al)d Call illClllCl~ ~he proced-lrc~: t:a~yl~t in O . S . E~dt~?~
4,116,903, incc~rpor~ted h~reln by r~ference a.<, wall ag thc
proc~dur~:, t~ught in the ~xr~mplQs holow.
~Ill low acid value product~; (thAt is, acid value~; It~r~i th~ln
~bout 20i of ~uch ~sction~ or such pl'~llCt.~ itl ccmhination w.itl~ tile
Dbove-ù~sc~ibe~ ~clditi~e~;, c,ln b~ r~d-lced in uolv~ t~i ~;ucll ~JS
xyl~ , tolue:)e, b~nzene, mine~al spirlts and the 1ilce. ~-~c):
prc~ducts c~n ~hot~ `oc allowe~l to air dry or ~orce(l to dry by bc~'cirlcJ
0 AS i~ wcll known in th~. art. ~ mino, ur ec~u.iv~l~l~t, agc!rl~:
wou~d pr~tc~ahly };e addcd to f,acili~dte ~ryincJ in th~d bake ~r~
~;y~ten~C;, In a prefer~e~l embodimetlt, thF~ w acid value product~:
of ~ectiol~ 2,c, can be dir.~ctly modified ~.ith e(cryl~c monomers,
oliqomers all~ po:lyme~rs to pro~.ll.lce ~ir ~ry, ~ake and wat~r-~ducibl~
coatinys.
Sultabl~ ac~rylic monomer~ li.gom~rs an~l polym~r~ inc.l.~cle
tho~:~ a~rylic, vinylic and ethylenically ~Ins~turat~d m~t~ric~
tau~ht to be ufi~ul with the high acld val~le pro~uct~i as wel]. as
the acl-ylia acids thernse]ves such as acrylic acld"nt?.thacrylic acl~
2a and itacor-ic acid.
.[n an~ her E)referr~d embvd11n(!nt~ eit.h~r the high or the 1C-JW
aai(l va1uc products of Section 2.c. ~an be furt~leI m~ 'ied by
d~ect flc~ryl i.c modieication. t)ir~ct acr~lic mv:llfl.ci.~ti.-JIl i5
typically c~nducted undor c:orl(litl~ns al~so well knt~wn in ~he ~rt,
including th~ pr~ced~lr,3s t~u:~ht in V.s. Patent.~ 4,735,'J~5 and
.
lB
,:
.. :
.7~ .JED 1~ 51 lC~CO~I E``'ECUrll-lE lEL ~`lr~ .~215-5~ '1 13 2 ti
,
~,~73,2~1, inCorporated ~le~ein ~y reEerQnoe, a~ well ~s by the
pro~dllr~s taught in the ~ nples below.
When acrylic modifyl~g the low aci~ value produc~, the
1ncorporatlon of A high level of aeid-~unc~ional acrylic materials
S w111 enable th~ ~inal, acrylic-modi~ied Goating produc~ to be
rsd-lcible ln water or other aqueou~ ~y6t~m~. Gene~lly, a~o~lnts
o~ acid-~'unctional acr~lic material~ ~reater than about 1.0~ by
welght of ~he total ~mo~nt o~ acrylic and ~other ethylenically
un~aturated m~terials w111 res~lt in a coating ~omposition whicll
i~ wate~ reducible. ~mounts less thah the above will generally
r~sult in ~oating~ which are not water reducible.
~ he coatings o~ this inventiOn can also be blehded with other
acrylic resins, alkyds, poly~ers and coatin~ resin sys~e~s.
~ he coatings of thi~ inv~ntion m~y ~ypic~lly be ~pplied to
: 15 any substrat~ ~u~h a8 met~l, pla~tlc~ wood, ~nd qla~3~ by b~ushing~
dipping, roll coa~ing, flo~ coa~in~, spraying or other me~hod
~onventionally ~mplo~ed in the coating industry.
ReprQsentative opacifying pigmen~.inolu~e white pigment~ such
a~ tlt~ium dloxide, zinc oxide, antimony oxlde, ~tc. and org~ic
~ inorganic chxom~ic pigmen~s suCII as iron oxide~ carbon black,
phthalooyanine blue, etc. The coatingS may also oon-tain extender
p~gment~ such as aalcium carbonate, clay, silic~, tala, ~tc.
~ he ~ollowing example9 have been ~elected to illustr~te
~cl~ic emhodiments and prac~ice~ o~ advant~g~ to a more comple~e
u~der~kandllly ~ the invqntloll. Unle~s otherwise ~tate~, "parts"
~all8 part~ w~l~ht ~nd "percent" i~ pe~cen~.-by~weigh~.
20- 13 l`J~C! 1?:5~ ID:CQN-EXECUTIOE TEL. ~`lC1:216-~66-21'13 l~k~ P21
~ ~ ~ 7 ~
r.~r~ur~Ly~:~c c~
~ h~gh c,c~ld ~c~ ., w~L.s.L Le~l~v.L~ . w
acaordin~ to t~.he followin5:t procedur~:
A 3 l, ~ k~d round b~t;tom flA~k Qquippod with ~ nort gAG I
~nechanical st1rrer, 13arr~tt tubR and Frledrich I s ac~nden~;er was
trlmetltylolpropane d i ~llyl ether, 5 . 3g o~ dibutyl tin vxi~e
o~oly~t ~n~l 37~ ~tylcne. 5~hc ~l~t~nt2 wo~ ec~t~:~;l t~ ~ao~ Ql~
un~il all con~QTl~s had melted and ~ clear ~olution was obtained.
The solution was cooled to ~Z5F ~nd ~90. 4g o~ tri~elletie
~nhydride, 344.~g dehydrated ~a~tor oil fatty acid and 65.8g
~1J1~ U11 f~Ly ~lv wire ~dded. T~le con~ents were nea~ea ~o
~70F ~nd held for an aeid value o~ between 60-~5 and a vi5c05ity
le~s than lo,QOOcp~ at 90~ i~ propylene gly~ol monop~opyl ether.
Ona~ r~ach~, heat waB removed and the contents allowed to cool.
rhe final resin product had an NVM of 89.~5/ a viscosity o~ 5300cps
(u~ing Brook~ield LVT-~3, 12rpm), acid v~lue ~ 6~, Mz o~ 428~, Mw
Qf 19~1, Mn of 103~ and Pd of 1.~7.
The resin was further reduced in w~ter by combining ~hP resin,
wa~er and triethylamine in ~h~ following amounts:
65g o~ re~in
65g o~ water
.lg o~ triethyla~nine.
~XAMPhE ~I: A~CO~IOLYSI~ OF PET
A high a~id ~lue, wat~r xeducible re~in w~ prepared
~cording to ~ho ~llowlny pxocedure:
2n
.~, . , J~ 2~-'93 1.IED l? ~ cn~-ExEcur ll~!E rEL ~lO 216-'~66-21~ 2 P22
( ,..3~7~ ~
A 31, 4~nec)ced round bottom ~ k e~uipped with ine.rt gas,
m~chanical ~tirrer, Ba~rett t~be ~nd Friedrich~S c~ndenser w~
charged with 54~.~g o~ polyethylen~ tereph~halate, 735.3g of
trimethylolpropane diallyl ether, 5.3g o~ di~utyl tin oxide
ue~t~lyo t ;~nd 55g xylene. ~ cc~ntent~3 were l~ e~ 4 60F ~r~d h~ld
until all cont~nt~ had melted and a clear sOlu~ion wa~ obtained.
The solution wa~ aooled to 325F and 290.0g o~ ~imelletic anhydride
a~d 409. 5g o hlgh content linolaic fatty acid ~Prifac 8~60) were
add~d. The con~bhts were h~at~d to 470F and held for an a~id ~lue
o~ ~etween 80-B5. Once r~a~h~d, he~t was rehloved and the content~
wed to cool. ~h~ final re~in product had an NvM of ~5.25, a
~is~osity o~ 18, ~OOCp5 (~sing ~rook~ield LVT#3, lZrpm), aci~ value
of B2, MZ o~ 36~9, Mw of 1643, Mn Of 919 ~nd Pd Of 1.79.
EXA~PL~ ALC~HOLYS~S OF P~T
A low aci~ value r~sin wa~ prepared acc~rding tQ th~ following
pro~edure:
A 31, 4~necked round bott~m flask eg~lipped with inert gas,
me~h~nical ~tirrer, Barrett tube and Friedrich's conden~7er was
oh:~rgod w~ ~h 1016 . 7~ o~ poly~thylen~ t~:;L~ tl~ , 414 . 0~ lL
ao prDp~ene gly~ol, sog o~ tlllnethylol~ ne diallyl ether, 5. sg o1
dibutyl t:in c~xide cataly~t and 4 Og xylene . The con~ents were
h~ted to 4GOF an~ held until all c~ntqn-t~ h~d melt~d and a clear
Yolution wa~; obtained. The ~olutlon w~ c:~ol~fl to 325F ~nd 59. og
trim~lleti~ ~nhydr.lLde wa~ added. Th~ nterlt~ Wel'~ heated to
~b 470F ~nd held ~or nn ac:id ~alue of l~ han lO. Once reac:lled,
h~a~ w~ r~moved und th~ contnn-t~ ~llow~d t:o cool. T~le ~inal resin
21
.. . . . . .
. . .
J~r~ 1'.5'~ I~'.CC~ ccur~ TC~ ~10.'11~ 5C~ '3'~ 3~
h `~ u 7 ~
product had an NVM of ~9.5, ~ v j~oo~i-ty gr~t~r than ~O,OOOcps
(u~ng Brookfield LV'~3, 12rpm), acid valu~ of 4.1~ Mz o~ 218~, Mw
of 134~, Mn o~ 84~ ~nd Pd of 1.5~.
I3XAMP~E IV; DIRECT P~CRYLI~ MuU~ A~ C)N
dOOg of the r~Eiin of Example III ~ncl 150g of Propasol
(propylene glycol monobutyl ether~ ~era charged te a re~c~ion
ve~el and h~ated to ~hn~ n~. Arl~ o th~ co~. o-~r ~ ~, 5
hour pe~iod wa6 ~B6g o~ lneth~l methacrylate, 43y of methacrylic
acid, 2~g o~ ~tyrene, sog o~ ethyl hexyl ~rylat~. A secon~ fecd
lO o~ 9g o~ t-~utyl perben~oate an~ lOOg of Propasol was added over
thQ ~ame time period. Upon complete addition of both ~eed~, a
~h~e of 1. ~g t-butyl per~en~o~te in ~Og o~ Propasol was add~d over
a ~.5 hour tim~ pe~iod. Heat was removed and the cont~n~s o~ th~
Yessel ~ilterad.
15 E~AMPLE V: AIR DRY COATI~G FORMULA
. A resin prepared according to ~he pro~edure of Exampl~ I can
be ~ormulated to a high solids, ~ol~ent~ba~ed air dry ~oating
having NV~ of ~0.55, VoC less t~an 250 g/l as ~ollow~:
Ih a hi~h speed dl~per~er, grtnd:
4~2.6g ReR~n of Ex~ple I
47 . 5 A~o~atio Naph~ha
- 7 . 7 Soya I~cithin
202 .~ R~t1le tit~nium dioxi~e
Run on high ~or 15 Dinu~s
25 Add 203.9 RQsin o~ Example I
1~.3 ~omatic Maphtha
1~2 1296 Cobalt Catal~t
29 . 5 1~ alc:ium Drier
2.1 Me~h~l ethyl ket~xi~nQ
30 ~1.9 ~roma~ia Napht~la
O~S ~e~o~m~r (Byk 0.~2)
~X~MP~E: ~X ~ I~A~E I~Y ENAM~ ~MUhA
~2
: ... : , ,. : .
, . ' ',
~q~.~J~N-20-'93 WED 12:55 . iD:CON EXECUTI~)E TEl NO:Z 16-566 .?.~ 02? P24, . ~.. .
~387~1~
f,
A re~3in p~epe~d according to th~3 procedure o~ Example III can
b~ formulated ~o a balce dry cs~ating ~aving PVC l~ ~ 5, NVM 80. 9 .
w~ight par gallon 11. 8 lhs/~al an~ ~oC Or 2 . 2~ lb~ al as ~ollows:
'r n ~ h ~ ~h o r~ ~ ~ ;L O p ~ J W l J ly .
S . 17g. lg ~sin of Example I~I
24 ~ O Prnr.a.snl P
423l ~u~ itanillm
Run to 7H ~e~an Grinc~)
~:tabll~ze l~0. V Propaso:l P
10 Thindown 241. 5 R~in o~ Exampl,e I~I
13Z. 7 Melamine
80. 2 PropasC~l P
.
- ~. ` .:, . .
,
~3
